j ourna l ho me pa g e: www.elsev ier .com/ locate /enbui ld
xperimental study of the cooling process of partially-melted sodiumcetate trihydrate
ing Jina,∗, Shuanglong Zhangb, Mario A. Medinac, Xiaosong Zhangb
Key Laboratory of Urban and Architectural Heritage Conservation of Ministry of Education, School of Architecture,outheast University, No. 2 Sipailou, Nanjing 210096, PR ChinaSchool of Energy and Environment, Southeast University, No. 2 Sipailou, Nanjing 210096, PR ChinaCivil, Environmental & Architectural Engineering Department, The University of Kansas, Lawrence 66045, KS, USA
r t i c l e i n f o
rticle history:eceived 25 October 2013ccepted 27 February 2014vailable online 12 March 2014
eywords:
a b s t r a c t
Actual phase transition processes of phase change materials (PCMs) are not fully isothermal. Furthermore,PCMs may exist in the partially-melted states during their applications. In this paper, the cooling processesof sodium acetate trihydrate (SAT), starting from three different states, namely not-melted, partially-melted, and fully-melted, were studied. It was found that the original state of SAT prior to phase transitionaffected its performance. When SAT was in the partially-melted state and the melting ratio was low, SAT
released latent heat during the cooling process and the degree of supercooling was relatively small. Whenthe melting ratio of SAT was high or the PCM was in its fully-melted state, the degree of supercoolingwas high and it did not release latent heat. The results also showed that the degree of supercooling ofpartially-melted SAT increased with the increase of maximum heating temperature sustained time priorto the cooling process.
Because of their high thermal storage density, latent heat stor-ge systems that use phase change materials (PCMs) are being usedn many fields, including buildings, as in the case of improving thehermal performance of building enclosures, solar energy storage,nd supplying free cooling and reducing energy consumption [1–6].
In theory, the phase transition process of PCMs is always consid-red to be isothermal or nearly isothermal. However, actual PCMsave their own phase change temperature ranges, which in someases may be more than 10 ◦C [7–9]. Fig. 1 shows the relation-hip between temperature and heat absorbed for ideal and actualCMs. As shown in the figure, actual phase transition processes areon-isothermal.
Based on the phase change temperature range of PCM, threeifferent states of any PCM can be identified as (1) when the PCMemperature is lower than its starting melting temperature, it iseemed to be in the not-melted state; (2) when the PCM temper-
ture is higher than its ending melting temperature, it is deemedo be in the fully-melted state; and (3) when the PCM tempera-ure is between its starting melting temperature and its ending
melting temperature, it is deemed to be in the partially-meltedstate. For storing the most thermal energy, it is recommendedthat the PCM starts the phase transition process from its solidstate (not-melted state) and ends in its fully-melted state. How-ever, because of several factors, a PCM may not always reach itsfully-melted state or may start a new cycle under a non-solidstate. For example, when a PCM is integrated into the enclosureof a building [10–13], if the outdoor was cloudy or the ambientair temperature was low, the PCM may not absorb sufficient heatand it may remain in a partially-melted state during the daytime.Because partially-melted states are common during the applica-tions of PCMs, it is important to understand the phase transitionprocesses of partially-melted PCMs and to evaluate the differencesbetween partially-melted PCMs and fully-melted PCMs.
Based on the situation described above, a kind of salt hydratePCMs, known as sodium acetate trihydrate (SAT), was selected tostudy the phase change characteristics of partially-melted statesvia differential scanning calorimeter (DSC) [14]. SAT has a natu-ral tendency to supercool during its solidification process [15–19],which affects its application. However, it was found that if SAT werecooled down from a partially-melted state, it would release latent
heat and quickly solidify without adding any nucleating agents [14].
Because the size of the sample in a DSC test is rather small andthe heating and cooling rates are linear, further investigation wasneeded to learn if actual phase transition conditions were similar
X. Jin et al. / Energy and Buildings 76 (2014) 654–660 655
Fig. 1. Relationship between temperature and heat absorbed for ideal and actualPCMs. ts: starting melting temperature; te: ending melting temperature.
tcw
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o DSC testing conditions. Therefore, in this paper, the cooling pro-esses of SAT in different states under environmental conditionsere studied and analyzed.
. Material and experimental set-up
The SAT used in this study was analytically pure. As shown in theig. 1(a) in [14], upon heating, SAT starts to melt at about 59.0 ◦C.he maximum heat flow point occurs at a temperature of about3.0 ◦C, which yields a calculated latent heat of fusion of 257.2 kJ/kgith a melting temperature range of 58.9–67.3 ◦C.
The experimental set-up was consisted of several calibrated testubes, filled with either SAT or water, placed inside a temperatureontrolled water bath. A scientific digital scale was used to accu-ately measure each sample before it was placed inside a calibratedest tube. In every experiment, two test tubes, one with 8 g of SATnd the other with 10 ml of water, were placed inside the temper-ture controlled water bath and heated for a period of time. After
heating process, the test tubes were then taken out of the waterath where they were allowed to cool down under ambient con-itions. Thermocouples with a maximum error of 0.1 ◦C were usedo measure the temperatures of SAT and water samples. Relevanthase change characteristics, such as the amount of heat release,uration of heat release, and degree of supercooling were obtainedia cooling curves of SAT.
Calibration tests were performed prior to each test to ensure thatny two test tubes would produce accurate results and to estab-ish baselines. That is, test tubes with the same volume water wereeated in the temperature controlled water bath and then allowedo cool down under ambient conditions. Fig. 2 shows the calibra-ion test results. As shown in the figure, the cooling curves of theest tubes were nearly identical, which set the thermal performanceaseline for the tests.
. Results and discussions
Three states for SAT were identified and used in the analyses: theot-melted state, the partially-melted state, and the fully-meltedtate. To compare the phase transition performances of SAT forhese states, a number of experiments were conducted, which
ainly differed according to the maximum heating temperaturesi.e., the controlled temperatures of water bath).
Fig. 2. Calibration results using water in two identical test tubes.
3.1. Effects of maximum heating temperature on the coolingprocess of SAT
Fig. 3 shows the cooling curves of SAT and water for severalmaximum heating temperatures. Fig. 4 shows the correspondingphotographs of the test tubes containing SAT during the cool-ing processes. In these experiments, the test tubes with SAT andwater were placed into the temperature controlled water bathand heated for 50 min. The selected maximum heating tempera-tures were 55.0 ◦C, 58.0 ◦C, 59.0 ◦C, 60.0 ◦C, 61.0 ◦C, 62.0 ◦C, 63.0 ◦C,64.0 ◦C, 65.0 ◦C, and 70.0 ◦C, respectively. The maximum tempera-ture of SAT during heating process in every experiment is shown inTable 1.
From Figs. 3(a) and 4(a), which were generated and photo-graphed, respectively, upon heating to and cooling down from amaximum heating temperature of 55.0 ◦C, it was observed that theSAT did not melt, and as a result, there was no latent heat releasedduring the cooling process. Furthermore, the variations of the tem-perature of SAT showed that its temperature dropped at a fasterrate than the temperature of water. The reason for this was that55.0 ◦C was lower than the starting melting temperature of the SAT.The photographs of Fig. 4(a) clearly show that there was no phasechange during the cooling process of the PCM. This situation wasconsidered to be in the not-melted state.
From Fig. 3(b)–(f), when the maximum heating temperatureswere between 58.0 ◦C and 62.0 ◦C, it was observed that the SATreleased increasing amounts of stored heat as the maximumheating temperatures increased. When the maximum heating tem-peratures were between 59.0 ◦C and 62.0 ◦C and after sustaining themaximum heating temperature for 50 min, SAT disassociated itselfinto two parts: one part was an aqueous solution, while the lowerpart was mainly a concentration of sodium acetate. When the testtube was exposed to ambient air outside the water bath, the SATreleased the latent heat it had absorbed during melting, and as aresult, it solidified. After several minutes, and after the SAT hadreleased the entire latent heat, as shown in Fig. 4(c)–(f), no fur-ther changes were observed during the remaining of the coolingprocess. According to the definition, the SAT in these experimentswas considered to be in the partially-melted state. In this range, themelting ratios were low.
As shown in Fig. 3(g)–(j), when the maximum heating temper-atures were 63.0 ◦C, 64.0 ◦C, 65.0 ◦C and 70.0 ◦C, and similar to thepreceding experiments, the SAT absorbed latent heat during the
first thermal cycle, so its rate of temperature increase was lowerthan that of the water. That is, the SAT temperature curve waslower than the water temperature curve during the heating process.
656 X. Jin et al. / Energy and Buildings 76 (2014) 654–660
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Fig. 3. Cooling curves of SAT for several maximum heating temperatures: (a) maximum heating temperature was 55.0 ◦C; (b) maximum heating temperature was 58.0 ◦C;( ◦ ◦ ◦
tm
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c) maximum heating temperature was 59.0 C; (d) maximum heating temperature waemperature was 62.0 ◦C; (g) maximum heating temperature was 63.0 ◦C; (h) maximum h
aximum heating temperature was 70.0 ◦C.
able 1aximum temperatures, degree of supercooling, and heat release times of SAT for severa
Maximum heating temperature (◦C) 55.0 58.0 59.0 60
Maximum temperature (◦C) 55.0 58.0 58.6 5Degree of supercooling (◦C) – 0 0
Heat release time (s) <20 240 490 72
s 60.0 C; (e) maximum heating temperature was 61.0 C; (f) maximum heatingeating temperature was 64.0 ◦C; (i) maximum heating temperature was 65.0 ◦C; (j)
X. Jin et al. / Energy and Buildings 76 (2014) 654–660 657
Fig. 4. Photographs of test tubes with SAT during the cooling processes: (a) maximum heating temperature was 55.0 ◦C; (b) maximum heating temperature was 58.0 ◦C;( ◦ re wa ◦ ◦
t um hm
HttthpiFtTssibb
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shows the similitude of the cooling curves for the water, exceptfor when the maximum heating temperature was 59.0 ◦C. This dis-crepancy occurred because the ambient air temperature was thehighest, the rate of water temperature decrease was the lowest
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c) maximum heating temperature was 59.0 C; (d) maximum heating temperatuemperature was 62.0 ◦C; (g) maximum heating temperature was 63.0 ◦C; (h) maxim
aximum heating temperature was 70.0 ◦C.
owever, during the subsequent cooling process it was observedhat no latent heat was released. This was evidenced by noting thathe cooling curves of both the SAT and the water were almost iden-ical. This meant that the SAT did not solidify when the maximumeating temperature was 63.0 ◦C and greater, up to 70.0 ◦C. Thehotographs of Fig. 4 show that the states and colors of the SAT
n Fig. 4(g)–(j) differed from the states and the colors of the SAT inig. 4(b)–(f). Because SAT did not release latent heat during the firsthermal cycle, it did not absorb latent heat in the subsequent cycle.hat is, in the second cycle, the SAT only absorbed and releasedensible heat. In this case, the SAT temperature variations wereimilar to those of the water. According to the definition, the SATn Fig. 3(g)–(i) was considered to be in the partially-melted state,ut with high melting ratios. The SAT in Fig. 3(j) was considered toe in the fully-melted state.
During these experiments, the water volumes in the test tubesid not vary and room air temperature variations were small.herefore, the released heat of SAT in these experiments could be
ompared with each other via the difference between water cool-ng curves and SAT cooling curves. For a more direct comparisonmong the heat released by the SAT in all the experiments, theAT and water cooling curves were grouped in Fig. 5. This figure
s 60.0 C; (e) maximum heating temperature was 61.0 C; (f) maximum heatingeating temperature was 64.0 ◦C; (i) maximum heating temperature was 65.0 ◦C; (j)
0 50 0 1000 150 0 2000 25 00 300 0 35 00
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Fig. 5. Grouped cooling curves for several maximum heating temperatures.
658 X. Jin et al. / Energy and Buildings 76 (2014) 654–660
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ig. 6. Cooling curves of SAT for several maximum heating temperature sustained
a) 70 min; (b) 80 min; (c) 90 min; (d) 100 min; (e) 110 min.
mong all the experiments. It was observed that when the maxi-um heating temperature range was between 58.0 ◦C and 62.0 ◦C,
he released heat increased with the increase of maximum heating
emperature. This was because when the maximum heating tem-eratures were higher, the SAT absorbed and released more latenteat.
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ig. 7. Cooling curves of SAT for several maximum heating temperature sustained times
a) 30 min; (b) 40 min; (c) 50 min; (d) 60 min; (e) 70 min.
prior to the cooling process when the maximum heating temperature was 60.0 ◦C:
Table 1 also shows the degree of supercooling and the heatrelease times observed for the SAT during these experiments.When the maximum heating temperature was 55.0 ◦C, because the
SAT did not melt, the heat release time was less than 20 s; whenthe maximum heating temperatures were 58.0 ◦C and 59.0 ◦C, theheat release time was between 240 and 490 s, but there was no
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prior to the cooling process when the maximum heating temperature was 62.0 ◦C:
X. Jin et al. / Energy and Buildings 76 (2014) 654–660 659
Table 2Degree of supercooling of SAT for several maximum heating temperature sustained times prior to the cooling process.
Maximum heating temperaturesustained time (s)
30 min 40 min 50 min 60 min 70 min 80 min 90 min 100 min 110 min
ig. 8. Grouped cooling curves for several maximum heating temperature sustainedimes prior to the cooling process when the maximum heating temperature was0.0 ◦C.
upercooling; when the maximum heating temperatures were0.0 ◦C, 61.0 ◦C and 62.0 ◦C, the heat release time was between 720nd 960 s and the degree of supercooling was between 4.5 ◦C and.6 ◦C; when the maximum heating temperatures were greaterhan 63.0 ◦C, the degree of supercooling was more than 50.0 ◦C,nd because there was no latent heat released during the coolingrocess, the heat release time was less than 20 s. Therefore, basedn these observations, it was concluded that when SAT meltedully, it exhibited severe supercooling problems and did not releaseatent heat. When SAT melted partially and the melting ratio wasow, SAT released latent heat during the cooling process and theegree of supercooling was small when compared to supercoolingalues of SAT at other maximum heating temperatures. Thesendings coincided with the DSC test results in [14], but becausehe experiments conditions, such as the mass of the sample, theooling rate, and the heating rate in the cooling experiment werell different from those in the DSC test, the values of degree ofupercooling, the phase transition performances of SAT in theooling experiment and the DSC test were not exactly the same.
.2. Effects of maximum heating temperature sustained time onhe cooling process of partially-melted SAT
Figs. 6 and 7 show the cooling curves of SAT and water foreveral maximum heating temperature sustained times whenhe maximum heating temperatures were 60.0 ◦C and 62.0 ◦C,espectively. Table 2 shows the degree of supercooling of SAT inhese experiments. It was observed that the degree of supercoolingncreased with the maximum heating temperature sustained time.
Similar to the results of Fig. 5, the SAT and water cooling curvesf Figs. 6 and 7 were grouped in the graphs of Figs. 8 and 9, respec-ively. Figs. 8 and 9 illustrate temperature variations during theooling process of the SAT as a function of time based on pre-eding maximum heating temperatures sustained times when theaximum heating temperatures were 60.0 ◦C (Fig. 8) and 62.0 ◦C
Fig. 9), respectively. The curves of both figures present the influ-nces that both the maximum heating temperature sustained timend the maximum heating temperature had on the cooling processf SAT. Fig. 8 shows that the amounts of released heat during these
Fig. 9. Grouped cooling curves for several maximum heating temperature sustainedtimes prior to the cooling process when the maximum heating temperature was62.0 ◦C.
experiments were close, which means that with the increaseof maximum heating temperature sustained time, although thedegree of supercooling increased, the amounts of released heatwere not affected when the melting ratios of SAT were low. How-ever, as shown in Fig. 9, it was found that the cooling processwas affected by the maximum heating temperature sustained time.When the maximum heating temperature was sustained for 40 minor 50 min, the SAT released relatively more latent heat. Whenthe maximum heating temperature was sustained for more than70 min, it was observed that SAT presented severe supercoolingproblems and did not release latent heat during the cooling process.These conclusions from Table 2 and Figs. 8 and 9 could be explainedvia the heterogeneous nucleation theory. The heterogeneousnucleation catalysts in the SAT tended to disappear under the con-dition with a higher maximum heating temperature and a longermaximum heating temperature sustained time, so the degree ofsupercooling increased with the increase of the maximum heat-ing temperature and the maximum heating temperature sustainedtime. The results were similar to the conclusions when the SAT wasfully-melted [19].
4. Conclusions
The cooling process of SAT for three states (i.e., not-melted,partially-melted, and fully-melted) was studied. It was found thatthe state of SAT prior to any phase transition affected its phase tran-sition performance. When the maximum heating temperature waslower than the starting melting temperature of SAT, which meantthe SAT was in the not-melted state, there was no phase changeand no latent heat was released; when the maximum heating tem-peratures were 58.0 ◦C and 59.0 ◦C, which meant the SAT was inthe partially-melted state and the melting ratios were low, theSAT released relatively small amounts of latent heat, but no super-cooling was observed; when the maximum heating temperatureswere 60.0 ◦C, 61.0 ◦C and 62.0 ◦C, which meant the SAT was in the
partially-melted state and the melting ratios were low, the degreeof supercooling was between 4.5 ◦C and 8.6 ◦C, but the SAT releasedrelatively more latent heat; when the maximum heating temper-atures were greater than 63.0 ◦C, which meant the melting ratios
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f the SAT were high or that the SAT was in the fully-melted state,t presented severe supercooling problems and it did not releaseatent heat. It was also found that the maximum heating tem-erature sustained time before the cooling process influenced theooling process and the degree of supercooling of partially-meltedAT.
cknowledgments
This research was supported by the National Natural Sci-nce Foundation of China under Grant No. 51308104, the Naturalcience Foundation of Jiangsu Province of China under Granto. BK20130625, the Specialized Research Fund for the Doctoralrogram of Higher Education under Grant No. 20130092120002,nd the China Postdoctoral Science Foundation under Grant No.013M530226.
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